Gold-Catalyzed Dehydrogenative Cycloaddition of Tethered 1,n-Dihydrodisilanes to Alkynes

被引：21

作者：

Kotzabasaki, Vasiliki ^{[1
]}

Lykakis, Ioannis N. ^{[2
]}

Gryparis, Charis ^{[1
]}

Psyllaki, Androniki ^{[1
]}

Vasilikogiannaki, Eleni ^{[1
]}

Stratakis, Manolis ^{[1
]}

机构：

[1] Univ Crete, Dept Chem, Iraklion 71003, Greece

[2] Aristotle Univ Thessaloniki, Dept Chem, Thessaloniki 54124, Greece

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 02期

关键词：

DOUBLE SILYLATION; TERMINAL ALKYNES; HYDROSILYLATION; NANOPARTICLES; ACETYLENES; COMPLEXES; OXIDATION; SI; HYDROSILANES; CYCLIZATION;

D O I：

10.1021/om3011678

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Gold nanoparticles supported on TiO2 (0.1-2% mol) catalyze at mild conditions the dehydrogenative addition of tethered 1,n-dihydrodisilanes, such as 1,1,3,3-tetramethyldisiloxane (1), 1,1,3,3-tetraphenyldisiloxane (2), 1,1,1,3,5,7,7,7-octamethyltetrasiloxane (3), 1,1,3,3,5,5-hexamethyltrisiloxane (4), and 1,2-bis(dimethylsilyl)benzene (5), to alkynes, forming cycloadducts and releasing H-2. Under the same conditions, polymeric methylhydrosiloxane is completely unreactive. For the majority of terminal alkynes and 1,n-dihydrodisilanes the yields are excellent (up to 99%). In general, terminal alkynes are more reactive as compared to internal. The reaction tolerates several functional groups and can be performed in a variety of solvents. In the case of 1,1,3,3-tetramethyldisiloxane, it is proposed that gold nanoparticles form intermediate cyclo-gold-tetramethyldisiloxane via a dehydrogenative pathway, which undergoes a formal [3+2] cycloaddition to alkynes.

引用

页码：665 / 672

页数：8

共 53 条

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